CN101037638A - Phosphamide ester extreme pressure anti-wear additives and preparation and application thereof - Google Patents
Phosphamide ester extreme pressure anti-wear additives and preparation and application thereof Download PDFInfo
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- CN101037638A CN101037638A CN 200610065738 CN200610065738A CN101037638A CN 101037638 A CN101037638 A CN 101037638A CN 200610065738 CN200610065738 CN 200610065738 CN 200610065738 A CN200610065738 A CN 200610065738A CN 101037638 A CN101037638 A CN 101037638A
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Abstract
The invention provides a extreme pressure antiwear agent with structure of right general formula, wherein R, R' is same or different alkyl group with C1-C20 linear chain or branched chain, asphalt base, aromatic group or aralkyl, R'' is amino (-NH2) or alkyl group with C1-C18 linear chain or branched chain, aromatic group, aralkyl or asphalt base. The antiwear agent is reacted by phosphorus trichloride and C1-C20 alcohol, hydrazine hydrate or C4-C18 orgnic amine. The antiwear agent of the invention can be used in lubrication oil and lubricant grease with 0.1-3.0 w% of recommeding amount.
Description
Technical field
The present invention relates to a kind of extreme pressure anti-wear additives that is used for lubricating oil and lubricating grease, and its production and application method.
Technical background
At present, the wear preventive additive that is widely used in lubricating oil (fat) mainly contains di-n-butyl phosphite (T304), tritolyl phosphate (T306), sulphur phosphoric acid-formaldehyde-amine condenses (T305), the multiple ester amine salt (T307) of sulphur phosphoric acid etc., kind is few, and shortcoming is arranged respectively, too high as the di-n-butyl phosphite activity, corrosion is more serious in the use; The tritolyl phosphate oil film strength is not high; The multiple ester amine salt of sulphur phosphoric acid-formaldehyde-amine condenses sulphur phosphoric acid has very smelly smell etc.
CN1465581A has reported the organic phosphoramide hydrochloride that contains following general formula, and the used as pesticides sterilant is used.
CN1176298A has reported a kind of thio-phosphamide ester anti-wear agent, and its general formula is
CN1324381A has reported the phosphamide fire-proof resin composition that contains following general formula, R
1Be amine residue, R
2And R
3Be alkoxyl group etc.
Summary of the invention
The invention provides a kind of good phosphamide ester extreme pressure wear preventive additive of abrasion resistance of low smell.
The present invention also provides the preparation method of above-mentioned additive.
The present invention also provides above-mentioned Application of Additives method.
Extreme pressure anti-wear additives provided by the invention is a kind of phosphamide (hydrazine) ester, has following formula:
R, R ' are C identical or inequality in the formula
1～C
20The alkyl of straight or branched, cycloalkyl, aryl or aralkyl, preferred C
4～C
16Alkyl, R " is amino (NH
2) or C
1～C
18Alkyl, aryl, aralkyl or the cycloalkyl of straight or branched, preferred amino or C
4～C
16Alkyl, phenyl or cycloalkyl.
The preparation method of extreme pressure anti-wear additives provided by the invention comprises:
Make phosphorus oxychloride and C
1～C
20Alcohols reacts down at-20 ℃～20 ℃ and generates intermediate phosphinylidyne dichloro; Add C again
1～C
20Alcohols is kept-20 ℃～20 ℃ and is continued reaction to generating the intermediate phosphoryl chloride; In phosphoryl chloride, add hydrazine hydrate or C
4～C
18Organic amine is warming up to 80 ℃～140 ℃ afterreactions to generating phosphamide (hydrazine) ester.
Specifically, anti-wear agent provided by the invention can prepare in accordance with the following methods:
(1) in the presence of organic solvent, by phosphorus oxychloride, C
1～C
20Alcohols reacts down in-20 ℃～20 ℃ and generates intermediate phosphinylidyne dichloro.This step reaction is quick thermopositive reaction, in order to ensure the purity of final product, preferably controls phosphorus oxychloride and C
1～C
20The mole number of alcohol is identical.
(2) in the presence of organic solvent, make intermediate phosphinylidyne dichloro and C
1～C
20Alcohols mixes, and adds acid binding agent in case of necessity, keeps-20 ℃～20 ℃ to generating the intermediate phosphoryl chloride; This step also is quick thermopositive reaction, adds the hydrogenchloride that acid binding agent can neutralization reaction generates, and promotes that molecular balance moves to the product direction, improves the yield of final product.In order to ensure the purity of final product, preferably control intermediate phosphinylidyne dichloro and C
1～C
20The mole number of alcohol is identical.
(3) in phosphoryl chloride, drip hydrazine hydrate or C
4～C
18Organic amine slowly is warming up to 80 ℃～140 ℃ and continues reaction 0.1～4 hour.In order to improve the yield of final product, can add acid binding agent in the reaction system.
Reaction finishes, and obtains the target compound crude product behind washing, drying, the desolventizing.Crude product can separate purification with silica gel column chromatography or underpressure distillation.
The add-on of the middle acid binding agent in step (2) and (3) can be 1～4 times of phosphorus oxychloride mole number, phosphorus oxychloride and hydrazine hydrate or C
4～C
18The theoretical molar ratio of organic amine is 1: 1, but hydrazine hydrate or C
4～C
18Organic amine can be excessive 5～10%, so that the phosphoryl chloride complete reaction.
Said organic solvent is the solvent that can dissolve phosphorus oxychloride, for example one or more in ether, tetrahydrofuran (THF), the toluene.The consumption of solvent is advisable with complete solubilizing reaction thing.
Said acid binding agent can be organic bases or mineral alkali, for example one or more in sodium hydroxide, Tetrabutyl amonium bromide, the triethylamine.
Among the said preparation method of the present invention, the intermediate of reaction also can separate earlier, carries out the next step again.
The recommendation consumption of anti-wear agent of the present invention in lubricating oil, lubricating grease is 0.1～3.0w%, is benchmark with the weight of lubricating oil, lubricating grease.
Anti-wear agent of the present invention is a kind of phosphorous, nitrogen additive, has the chemically reactive of appropriateness, and oil soluble is good, with other additive good compatibleness is arranged, and does not contain element sulphur, and no specific peculiar smell can reduce the pollution to air.Anti-wear agent supporting capacity of the present invention is much higher than tritolyl phosphate (T306), have rust-preventing characteristic and copper corrosion rejection simultaneously, it is a kind of multipurpose additive, be applied in gear oil and the antiwear hydraulic oil, have good wear resistance, also can be applicable in lubricating grease, automobile automatic drive liquid and the hydraulic efficiency oil simultaneously.
Description of drawings
Fig. 1 is the infrared spectrogram of the n-octyl dodecyl phosphinylidyne hydrazine ester of example 1 preparation.Infrared spectrogram to n-octyl dodecyl phosphinylidyne hydrazine is made a concrete analysis of, wherein, and 1018.4 and 1097.1cm
-1Be that (the absorption peak scope of P-O-C is at 970～1150cm for the absorption peak of P-O-C and P-N
-1, the absorption peak scope of P-N is at 930～1110cm
-1), 1260.6cm
-1Be the absorption peak of P=O, 1604.2cm
-1Be NH
2The formation vibration peak.2958.8,2855.2,1461.8 and 1378.7cm
-1Be-CH
3Absorption peak, 2925.0 and 728.7cm
-1Be NH
2Absorption peak.By Infrared spectroscopy, can roughly determine the structure of n-octyl dodecyl phosphinylidyne hydrazine ester.
Fig. 2 is the infrared spectrogram of the diisooctyl phosphinylidyne hydrazine ester of example 2 preparations.Among Fig. 2, the infrared spectrogram shape basically identical of the n-octyl dodecyl phosphinylidyne hydrazine ester among diisooctyl phosphinylidyne hydrazine ester and Fig. 1 shows that the two is same compounds.
Fig. 3 is the infrared spectrogram of the di-n-butyl phosphinylidyne amino dodecane ester of example 3 preparations.Among Fig. 3,1026.9,978.5 and 1157.9cm
-1Be that (the absorption peak scope of P-O-C is at 970～1150cm for the absorption peak of P-O-C and P-N
-1, the absorption peak scope of P-N is at 930～1110cm
-1), 1233.2cm
-1Be the absorption peak of P=O, 1617.9cm
-1Be NH
2The formation vibration peak.2959.5,2868.4,1463.0 and 1381.4cm
-1Be-CH
3Absorption peak, 2925.0 and 728.7cm
-1Be-absorption peak of NH.By Infrared spectroscopy, can roughly determine the structure of di-n-butyl phosphinylidyne amino dodecane ester.
Fig. 4 is the infrared spectrogram of the di-n-butyl phosphinylidyne hexahydroaniline ester of example 4 preparations.Among Fig. 4,1070.3 and 940.4cm
-1Be that (the absorption peak scope of P-O-C is at 970～1150cm for the absorption peak of P-O-C and P-N
-1, the absorption peak scope of P-N is at 930～1110cm
-1), 1222.0cm
-1Be the absorption peak of P=O, 1634.9cm
-1Be NH
2The formation vibration peak.2866.1,1455.0 and 1384.8cm
-1Be-CH
3Absorption peak, 2927.6 and 724.6cm
-1Be NH
2Absorption peak.By Infrared spectroscopy, can roughly determine the structure of di-n-butyl phosphinylidyne hexahydroaniline ester.
Fig. 5 is the infrared spectrogram of the normal-butyl n-octyl phosphinylidyne diboronic ester of example 5 preparations.Among Fig. 5,1005.3cm
-1Big peak be that (the absorption peak scope of P-O-C is at 970～1150cm for the absorption peak of P-O-C and P-N
-1, the absorption peak scope of P-N is at 930～1110cm
-1), 1225.2cm
-1Be the absorption peak of P=O, 1603.6cm
-1Be NH
2The formation vibration peak.2925.5,2854.6,1500.0 and 1421.5cm
-1Be-CH
3Absorption peak, 2925.5,750.5 and 723.0cm
-1Be NH
2Absorption peak.By Infrared spectroscopy, can roughly determine the structure of normal-butyl n-octyl phosphinylidyne diboronic ester.
Embodiment
The invention will be further described below by example, but following example does not limit the invention.
The present invention is about lubricating oil supporting capacity and abrasion resistance pipette method (tetra-ball machine test method, GB/T 3142 and SH/T 0189): the supporting capacity of lubricating oil is with last non seizure load P
BValue representation, wear resistance is represented with wear scar diameter.The supporting capacity of lubricating oil is good more, P
BBe worth big more; Wear resistance is good, and wear scar diameter is little.
Example 1
Get the 0.3mol phosphorus oxychloride, 200ml toluene, under 0 ± 5 ℃ of temperature, stir adding 0.3mol n-Octanol, stir adding 0.3mol lauryl alcohol and 0.6mol triethylamine after 3 hours, add the 0.33mol hydrazine hydrate after stirring in 3 hours, reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature, washing, drying is purified, gained water white transparency thick liquid is a wear preventive additive n-octyl dodecyl phosphinylidyne hydrazine ester, and code name is A1.A1 is joined in the N46 base oil by 0.50w%, carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0w%, carry out the four-ball tester evaluation, the results are shown in Table 2.
Example 2
Get the 0.3mol phosphorus oxychloride, the 200ml tetrahydrofuran (THF), under 0 ± 5 ℃ of temperature, stir adding 0.3mol isooctyl alcohol, stir adding 0.3mol isooctyl alcohol and 0.6mol triethylamine after 3 hours, add the 0.33mol hydrazine hydrate after stirring in 3 hours, reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature, washing, drying is purified, the light yellow transparent liquid of gained is a wear preventive additive diisooctyl base phosphinylidyne hydrazine ester, and code name is A2.A2 is joined in the N46 base oil by 0.50w%, carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0w%, carry out the four-ball tester evaluation, the results are shown in Table 2.
Example 3
Get the 0.3mol phosphorus oxychloride, the 150ml ether stirs adding 0.3mol propyl carbinol under 0 ± 5 ℃ of temperature, stirs after 3 hours to add 0.3mol propyl carbinol and 0.4mol triethylamine, after 3 hours, separates, and boils off solvent, obtains the intermediate phosphoryl chloride.Phosphoryl chloride, 150ml toluene are inserted there-necked flask, adding 0.3mol carbon number is 12 the primene JM-T (Primene 81-R), stir and add the 0.3mol triethylamine, reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature, washing, drying is purified, the gained yellow transparent liquid is a wear preventive additive di-n-butyl phosphinylidyne amino dodecane ester, and code name is A3.A3 is joined in the N46 base oil by 0.50w%, carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0w%, carry out the four-ball tester evaluation, the results are shown in Table 2.
Example 4
Get the 0.3mol phosphorus oxychloride, the 150ml ether stirs adding 0.3mol propyl carbinol under 0 ± 5 ℃ of temperature, stirs after 3 hours to add 0.3mol propyl carbinol and 0.4mol triethylamine, after 3 hours, separates, and boils off solvent, obtains the intermediate phosphoryl chloride.Phosphoryl chloride, 150ml toluene are inserted there-necked flask; add the 0.3mol hexahydroaniline; stir and add the 0.3mol triethylamine; reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature; washing, drying is purified; gained yellow transparent thick liquid is a wear preventive additive di-n-butyl phosphinylidyne hexahydroaniline ester, and code name is A4.A4 is joined in the N46 base oil by 0.50w%, carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0w%, carry out the four-ball tester evaluation, the results are shown in Table 2.
Example 5
Get the 0.3mol phosphorus oxychloride, 200ml toluene, under 0 ± 5 ℃ of temperature, stir adding 0.3mol n-Octanol, stir adding 0.3mol propyl carbinol and 0.6mol triethylamine after 3 hours, add 0.3mol aniline after stirring in 3 hours, reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature, washing, drying is purified, the brown transparent liquid of gained is a wear preventive additive normal-butyl n-octyl phosphinylidyne diboronic ester, and code name is A5.A5 is joined in the N46 base oil by 0.50w%, carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0w%, carry out the four-ball tester evaluation, the results are shown in Table 2.
Table 1 adds the four-ball tester evaluation result of 0.5w% anti-wear agent
| Oil sample * | Anti-wear agent | P BValue (N) | Wear scar diameter (mm) |
| The N46 base oil | A1 | 833 | 0.47 |
| The N46 base oil | A2 | 1274 | 0.42 |
| The N46 base oil | A3 | 931 | 0.45 |
| The N46 base oil | A4 | 882 | 0.34 |
| The N46 base oil | A5 | 980 | 0.52 |
| The N46 base oil | T306 | 637 | 0.67 |
| The N46 base oil | T307 | 980 | 0.49 |
*The condition of measuring wear scar diameter is load 392N, rotating speed 1200rpm, time 60min.
Table 2 adds 1.0w% anti-wear agent four-ball tester evaluation result
| Oil sample * | Anti-wear agent | P BValue (N) | Wear scar diameter (mm) |
| The N46 base oil | A1 | 1127 | 0.48 |
| The N46 base oil | A2 | 1421 | 0.43 |
| The N46 base oil | A3 | 931 | 0.46 |
| The N46 base oil | A4 | 980 | 0.32 |
| The N46 base oil | A5 | 1127 | 0.50 |
| The N46 base oil | T306 | 637 | 0.62 |
| The N46 base oil | T307 | 1078 | 0.48 |
*The condition of measuring wear scar diameter is load 392N, rotating speed 1200rpm, time 60min.
Claims (10)
1. extreme pressure anti-wear additives has following formula:
R, R ' are C identical or inequality in the formula
1～C
20The alkyl of straight or branched, cycloalkyl, aryl or aralkyl, R " is amino or C
1～C
18Alkyl, aryl, aralkyl or the cycloalkyl of straight or branched.
2. according to the described extreme pressure anti-wear additives of claim 1, it is characterized in that R, R ' are C
4～C
16Alkyl, R " is amino or C
4～C
16Alkyl, phenyl or cycloalkyl.
3. the preparation method of the described extreme pressure anti-wear additives of claim 1, comprising: (1) makes phosphorus oxychloride and C
1～C
20Alcohols reacts down at-20 ℃～20 ℃ and generates intermediate phosphinylidyne dichloro; (2) add C
1～C
20Alcohols is kept-20 ℃～20 ℃ reactions to generating the intermediate phosphoryl chloride; (3) add hydrazine hydrate or C
4～C
18Organic amine is warming up to 80 ℃～140 ℃ reactions to generating phosphoramidate or phosphinylidyne hydrazine ester.
4. according to the described preparation method of claim 3, it is characterized in that add acid binding agent in step (2) and (3), add-on is 1～4 times of phosphorus oxychloride mole number.
5. according to the described preparation method of claim 4, it is characterized in that said acid binding agent is organic bases or mineral alkali.
6. according to the described preparation method of claim 5, it is characterized in that said acid binding agent is one or more in sodium hydroxide, Tetrabutyl amonium bromide, the triethylamine.
7. according to the described preparation method of claim 1, it is characterized in that, add in the reaction and can dissolve the organic solvent of phosphorus oxychloride.
8. according to the described preparation method of claim 7, it is characterized in that said organic solvent is one or more in ether, tetrahydrofuran (THF), the toluene.
9. the application of the described extreme pressure anti-wear additives of claim 1 in lubricating oil, lubricating grease.
10. according to the described preparation method of claim 9, it is characterized in that the consumption of extreme pressure anti-wear additives in lubricating oil, lubricating grease is 0.1～3.0w%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031718A (en) * | 2014-06-19 | 2014-09-10 | 天津舜能化学品有限公司 | Aliphatic amine ester boride lubricating oil additive and preparation method thereof |
| CN106244293A (en) * | 2011-09-15 | 2016-12-21 | 雅富顿公司 | Lubricant compositions |
| CN108624381A (en) * | 2018-06-07 | 2018-10-09 | 中国林业科学研究院林产化学工业研究所 | A kind of water base lubricant and preparation method thereof |
| CN108793807A (en) * | 2018-07-11 | 2018-11-13 | 济南大学 | A kind of bridge light reinforced concrete phosphamide corrosion inhibitor and preparation method thereof |
| CN113480572A (en) * | 2021-07-02 | 2021-10-08 | 新乡市瑞丰新材料股份有限公司 | Preparation method of phosphorus-nitrogen type ashless extreme pressure antiwear agent and extreme pressure antiwear lubricating oil |
| CN113735904A (en) * | 2021-09-17 | 2021-12-03 | 南京自一界科技研发有限公司 | Preparation method of lubricating additive |
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2006
- 2006-03-15 CN CNB2006100657381A patent/CN100487094C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106244293A (en) * | 2011-09-15 | 2016-12-21 | 雅富顿公司 | Lubricant compositions |
| CN104031718A (en) * | 2014-06-19 | 2014-09-10 | 天津舜能化学品有限公司 | Aliphatic amine ester boride lubricating oil additive and preparation method thereof |
| CN104031718B (en) * | 2014-06-19 | 2016-02-03 | 天津舜能化学品有限公司 | A kind of boronation aliphatic amide ester lubricating additive and preparation method thereof |
| CN108624381A (en) * | 2018-06-07 | 2018-10-09 | 中国林业科学研究院林产化学工业研究所 | A kind of water base lubricant and preparation method thereof |
| CN108624381B (en) * | 2018-06-07 | 2020-12-22 | 中国林业科学研究院林产化学工业研究所 | Water-based lubricant and preparation method thereof |
| CN108793807A (en) * | 2018-07-11 | 2018-11-13 | 济南大学 | A kind of bridge light reinforced concrete phosphamide corrosion inhibitor and preparation method thereof |
| CN113480572A (en) * | 2021-07-02 | 2021-10-08 | 新乡市瑞丰新材料股份有限公司 | Preparation method of phosphorus-nitrogen type ashless extreme pressure antiwear agent and extreme pressure antiwear lubricating oil |
| CN113735904A (en) * | 2021-09-17 | 2021-12-03 | 南京自一界科技研发有限公司 | Preparation method of lubricating additive |
| CN113735904B (en) * | 2021-09-17 | 2023-10-24 | 南京自一界科技研发有限公司 | Preparation method of lubricating additive |
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